Adhesion promoter and ink composition

ABSTRACT

An ink composition and an adhesion promoter are provided. The adhesion promoter is suitable for production while remaining the stronger adhesion. The adhesion promoter is formed by the reaction of at least one alpha hydroxy acid and at least one alpha hydroxy acid ester with the metal alkoxide. More specifically, by combining the renewable and green alpha hydroxy acid and safer plasticizing alpha hydroxy acid ester as reagent to react with the metal alkoxide, the eco-friendly and non-toxic adhesion promoter with superior adhesion for use in ink composition can be obtained. The ink composition includes the adhesion promoter, a pigment, a polymeric binder, and a solvent for the polymeric binder. The ink composition is odorless and colorless, and shows good wet crinkle resistance. Especially, the ink composition is suitable for printing on the food package.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. Provisional Application Ser. No. 62/401,905, filed Sep. 30, 2016, which is herein incorporated by reference.

BACKGROUND Field of Invention

The present invention relates to an ink composition and an adhesion promoter. More particularly, the present invention relates to an ink composition and an adhesion promoter for use in ink composition, wherein the adhesion promoter includes a reaction product of a metal alkoxide and a mixture of at least one alpha hydroxy acid and at least one alpha hydroxy acid ester.

Description of Related Art

Adhesion promoters have long been used in inks to promote adhesion properties to enable the inks to adhere to a variety of substrates and thus meet requirements of customers and end-users.

However, in some printing ink formulation processes, adhesion promoters such as titanium acetylacetonates tend to impart undesirable by-products to the ink. These by-products may have undesired yellow color and odor and thus adversely influence the resulting inks. Moreover, the toxic acetylacetone derivative ingredient is not suitable for being printed on food package due to potential migration problem. Based on above, it is required adhesion promoters with superior adhesion and safety to satisfy the current industrial needs.

SUMMARY

The present disclosure provides an adhesion promoter. The adhesion promoter includes a reaction product of a metal alkoxide and a mixture of at least one alpha hydroxy acid and at least one alpha hydroxy acid ester. More specifically, by combining the renewable and green alpha hydroxy acid and safer plasticizing alpha hydroxy acid ester as reagent to react with the metal alkoxide, the eco-friendly and non-toxic adhesion promoter with superior adhesion for use in ink composition can be obtained. The metal alkoxide has a formula of M(OR₁)(OR₂)(OR₃)(OR₄), wherein M is titanium, zirconium, or aluminum, and R₁, R₂, R₃, and R₄ are independently C₁ to C₈ alkyl group. The alpha hydroxy acid is selected from the group consisting of glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. The alpha hydroxy acid ester is selected from the group consisting of glycolic acid ester, lactic acid ester, malic acid ester, tartaric acid ester, and citric acid ester.

In some embodiments, the glycolic acid ester has a formula of CH₂OH(COOR₅), and R₈ is C₂ to C₆ alkyl group.

In some embodiments, the lactic acid ester has a formula of C₂H₄OH(COOR₆), and R₆ is C₂ to C₆ alkyl group.

In some embodiments, the malic acid ester has a formula of C₂H₃OH(COOR₇)(COOR₈), R₇ and R₈ are independently H atom or C₂ to C₆ alkyl group, and one of R₇ and R₈ is an alkyl group.

In some embodiments, the tartaric acid ester has a formula of C₂H₂(OH)₂(COOR₉)(COOR₁₀), R₉ and R₁₀ are independently H atom or C₂ to C₆ alkyl group, and one of R₉ and R₁₀ is an alkyl group.

In some embodiments, the citric acid ester has a formula of C₃H₄OH(COOR₁₁)(COOR₁₂)(COOR₁₃), R₁₁, R₁₂ and R₁₃ are independently H atom or C₂ to C₆ alkyl group, and one of R₁₁, R₁₂ and R₁₃ is an alkyl group.

In some embodiments, the mixture further comprises water.

In some embodiments, the mixture has a carboxylic acid number of from about 50 mg KOH/g to about 400 mg KOH/g.

In some embodiments, a ratio of a total mole of the at least one alpha hydroxy acid and the at least one alpha hydroxy acid ester to a mole of the metal alkoxide is 0.2 to 4:1.

The present disclosure provides an ink composition. The ink composition includes a pigment, a polymeric binder, a solvent for the polymeric binder, and an adhesion promoter including a reaction product of a metal alkoxide and a mixture of at least one alpha hydroxy acid and at least one alpha hydroxy acid ester. The metal alkoxide has a formula of M(OR₁)(OR₂)(OR₃)(OR₄), wherein M is titanium, zirconium, or aluminum, and R₁, R₂, R₃, and R₄ are independently C₁ to C₈ alkyl group. The alpha hydroxy acid is selected from the group consisting of glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. The alpha hydroxy acid ester is selected from the group consisting of glycolic acid ester, lactic acid ester, malic acid ester, tartaric acid ester, and citric acid ester.

In some embodiments, the adhesion promoter is present at a concentration of from 1% to 20% by weight, based on the total weight of the ink composition.

In some embodiments, the polymeric binder has at least one functional group selected from the group consisting of hydroxyl group (—OH), amino group (—NH₂), carboxyl group (—COOH), cyanate group (—NCO), and ester group.

These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims.

It is to be understood that both the foregoing general description and the following detailed description are by examples, and are intended to provide further explanation of the invention as claimed.

DETAILED DESCRIPTION

The use of examples anywhere in this specification including examples of any terms discussed herein is illustrative only, and in no way limits the scope and meaning of the invention or of any exemplified term. Likewise, the invention is not limited to various embodiments given in this specification.

Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure, and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the singular forms “a,” “an” and “the” are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms “comprises” and/or “comprising”, or “includes” and/or “including” or “has” and/or “having” when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

The present disclosure provides an ink composition and an adhesion promoter for use in ink composition. More specifically, the adhesion promoter is for formulating ink composition. In some embodiments, the adhesion promoter is used in printing ink composition. The printing ink composition may be used for printing paper, foil, and plastic substrates, especially the plastic films for food packaging or flexible substrates. The material of plastic substrate includes but not limited to polyester, polyethylene, polypropylene, and co-extruded polyolefin.

Compared to paper or foil, the adhesion between printing ink composition and plastic films is weaker due to their extreme low surface energy characteristics. Therefore, the printing ink composition must need an adhesion promoter which can improve the adhesion on plastic films for industrial production.

Both physical and chemical interaction induced by adhesion promoters can enhance the adhesion between printing ink and plastic films. The adhesion promoter improves the adhesion by providing the chemical bond formation between the plastics films and printing ink. This chemical reaction is also called crosslinking reaction. A metal alkoxide can be chosen as adhesion promoter because of the chemical bond formation ability with oxygen-rich species (e.g. the binder in printing ink). However, the metal alkoxide is too reactive with the oxygen-rich species; therefore, the oxygen-rich species added with the metal alkoxide is too stable and has poor fluidity. Accordingly, the metal alkoxide cannot be used as adhesion promoter alone. In order to solve the above issue, the metal alkoxide can be chelated by at least one ligand formed from a mixture of at least one alpha hydroxy acid and at least one alpha hydroxy acid ester to strike a balance between reactivity and stability after mixing with the printing ink. The alpha hydroxy acid and alpha hydroxy acid ester are lower toxicity substance. It states different combinations of alpha hydroxy acid and alpha hydroxy acid ester can be chosen according to the need of formulator. The reaction product of the metal alkoxide, the at least one alpha hydroxy acid, and the at least one alpha hydroxy acid ester, can retain the adhesion-improving ability and lower toxicity by controlling the residual alkoxy group on metal and the carboxylic acid groups in the mixture. Also, controlling of the alkyl group on the alpha hydroxy acid ester can increase the compatibility to the plastic films and polymer binders in printing ink.

The adhesion promoter of the present disclosure includes a reaction product of a metal alkoxide and an acid ester mixture including at least one alpha hydroxy acid and at least one alpha hydroxy acid ester. The at least one alpha hydroxy acid includes one or more alpha hydroxy acids, and the at least one alpha hydroxy acid ester includes one or more alpha hydroxy acid esters.

In other words, the adhesion promoter is formed by reacting the at least one alpha hydroxy acid and the at least one alpha hydroxy acid with the metal alkoxide. In some embodiments, the step of reacting the at least one alpha hydroxy acid and the at least one alpha hydroxy acid with the metal alkoxide is performed at a temperature from about 20° C. to about 200° C. In some other embodiments, the temperature is from about 50° C. to about 120° C.

The metal alkoxide has a formula of M(OR₁)(OR₂)(OR₃)(OR₄), wherein M is titanium, zirconium, or aluminum, and R₁, R₂, R₃, and R₄ are independently C₁ to C₈ alkyl group. More specifically, R₁, R₂, R₃, and R₄ are independently linear or branched alkyl group. In some embodiments, R₁, R₂, R₃, and R₄ are independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, tent-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, hexyl, heptyl, or octyl. In some embodiments, R₁, R₂, R₃, and R₄ are independently propyl or butyl, and R₁, R₂, R₃, and R₄ include at least one propyl and at least one butyl; therefore, the metal alkoxide is propyl butyl metal alkoxide. In some other embodiments, R₁, R₂, R₃, and R₄ are n-propyl, and thus the metal alkoxide is tetra n-propyl metal alkoxide. In still some other embodiments, R₁, R₂, R₃, and R₄ are isopropyl, and thus the metal alkoxide is tetra isopropyl metal alkoxid.

The alpha hydroxy acid is selected from the group consisting of glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid. The alpha hydroxy acid ester is selected from the group consisting of glycolic acid ester, lactic acid ester, malic acid ester, tartaric acid ester, and citric acid ester.

In some embodiments, the glycolic acid ester has a formula of CH₂OH(COOR₅), and R₅ is C₂ to C₆ alkyl group. In some embodiments, the lactic acid ester has a formula of C₂H₄OH(COOR₆), and R₆ is C₂ to C₆ alkyl group. In some embodiments, the malic acid ester has a formula of C₂H₃OH(COOR₇)(COOR₈). R₇ and R₈ are independently H atom or C₂ to C₆ alkyl group, and one of R₇ and R₈ is an alkyl group. In some embodiments, the tartaric acid ester has a formula of C₂H₂(OH)₂(COOR₉)(COOR₁₀). R₉ and R₁₀ are independently H atom or C₂ to C₆ alkyl group, and one of R₉ and R₁₀ is an alkyl group. In some embodiments, the citric acid ester has a formula of C₃H₄OH(COOR₁₁)(COOR₁₂)(COOR₁₃). R₁₁, R₁₂ and R₁₃ are independently H atom or C₂ to C₆ alkyl group, and one of R₁₁, R₁₂ and R₁₃ is an alkyl group. In some embodiments, R₅ to R₁₃ are independently linear or branched alkyl group. In some embodiments, R₅ to R₁₃ are independently ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tent-butyl, n-pentyl, tert-pentyl, neopentyl, isopentyl, sec-pentyl, 3-pentyl, or hexyl.

In some embodiments, the carboxylic acid number of the acid ester mixture is in the range of from about 50 mg KOH/g to about 400 mg KOH/g.

In some embodiments, a ratio of a total mole of the at least one alpha hydroxy acid and the at least one alpha hydroxy acid ester to a mole of the metal alkoxide is 0.2 to 4:1. In some other embodiments, the ratio is 1 to 2:1.

It is noted that the adhesion promoter of the present disclosure includes the reaction product of the metal alkoxide and the acid ester mixture. More specifically, after the reaction of the metal alkoxide and the acid ester mixture, the ingredient in the acid ester mixture would bind to the metal atom to form metal chelate. For example, when one carboxylic acid group on the citric acid is reacted with the metal alkoxide, the metal alkoxide loses one alkoxy group (for example, OR₁, OR₂, OR₃, or OR₄), and the citric acid loses one hydrogen atom of the carboxylic group and then bonds with the metal atom of the metal alkoxide. Further, for example, when the tri-alkyl citrate is reacted with the metal alkoxide, the tri-alkyl citrate may bond with the metal atom of the metal alkoxide with its ester groups by transesterification. More specifically, the alkoxy group of the metal alkoxide may be replaced with the ester group of the tri-alkyl citrate. The way of the mono-alkyl citrate and the di-alkyl citrate binding with the metal alkoxide can be inferred from the descriptions above, and therefore is not repeated herein. It is noted that one metal alkoxide can react with one reactant or at least two reactants simultaneously. If the metal alkoxide react with at least two reactants, the at least two reactants can be different. For example, the alpha hydroxy acid is citric acid, and the at least one alpha hydroxy acid ester includes mono-alkyl citrate, di-alkyl citrate, tri-alkyl citrate, or a combination thereof. In some embodiments, the metal alkoxide reacts with the citric acid and the mono-alkyl citrate to form a metal chelate. In some other embodiments, the metal alkoxide reacts with the mono-alkyl citrate and the di-alkyl citrate to form a metal chelate. In still some other embodiments, the metal alkoxide reacts with the citric acid, the mono-alkyl citrate, and the di-alkyl citrate to form a metal chelate.

In some embodiments, the acid ester mixture further includes water. More specifically, the adhesion promoter includes a reaction product of a metal alkoxide and an acid ester mixture including at least one alpha hydroxy acid, at least one alpha hydroxy acid ester, and water. It is noted that the metal chelates having alkoxy group, which are reaction products of the metal alkoxides and the acid ester mixture, or the metal alkoxides, may react with water, and thus the alkoxy groups of the metal chelates or the metal alkoxides may be replaced with hydroxyl groups (—OH). After that, the hydrolyzed product can further react with another metal alkoxides or hydrolyzed metal alkoxides to form a larger molecule, together with the loss of water or alcohols. This reaction is a condensation reaction. Accordingly, the reaction product of the metal alkoxide and the acid ester mixture including water may include many kinds of condensation compounds (e.g. condensed metal chelates). The above condensation reaction can be further illustrated by the following example. For example, after two metal chelate having a formula of M(L₁)(L₂)(L₃)(OR) react with water, two metal chelate having a formula of M(L₁)(L₂)(L₃)(OH) are formed, wherein L₁, L₂, and L₃ are independently a ligand formed from a citric acid, a mono-alkyl citrate, a di-alkyl citrate, or a tri-alkyl citrate, and OR is an alkoxy group. After that, the two metal chelate having a formula of M(L₁)(L₂)(L₃)(OH) may combine to form M(L₁)(L₂)(L₃)—O-M(L₁)(L₂)(L₃) and water.

The ink composition of the present disclosure includes a pigment, a polymeric binder, a solvent for the polymeric binder, and an adhesion promoter. In some embodiments, the adhesion promoter is present at a concentration of from 1% to 20% by weight, based on the total weight of the ink composition.

In the present disclosure, the ink composition includes one or more pigments. The pigments may be inorganic pigment or organic pigment. In some embodiments, the pigment is TiO₂. In some embodiments, the polymeric binder has at least one functional group selected from the group consisting of hydroxyl group (—OH), amino group (—NH₂), carboxyl group (—COOH), cyanate group (—NCO), and ester group. For example, the polymeric binder includes polyester resin, polyamide resin, polyurethane resin, polyurethane-urea resin, nitrocellulose, polyacrylate resin, polyol resin, polyester polyol resin, polyether polyol resin, ketonic resin, ketone-formaldehyde copolymer, polyvinyl alcohol, or a combination thereof. In some embodiments, the polyacrylate resin is polymethylmethacrylate (PMMA). In some embodiments, the solvent for the polymeric binder includes alcohol, ester, ketone, hydrocarbon solvent, or a combination thereof. For example, the alcohol is ethanol, propan-1-ol, isopropanol, or n-butanol. For example, the ester is ethyl acetate, propyl acetate, or n-butyl acetate. For example, the ketone is acetone, butanone, or cyclohexanone. For example, the hydrocarbon solvent is n-hexane or n-heptane.

The disclosure is further illustrated by the following examples, which are not to be construed as limiting this disclosure in scope or spirit to the specific procedures herein described. It is to be understood that the examples are provided to illustrate certain embodiments and that no limitation to the scope of the disclosure is intended. It is to be further understood that resort may be had to various other embodiments, modifications, and equivalents thereof which may suggest themselves to those skilled in the art without departing from the spirit of the present disclosure and/or scope of the appended claims.

EXAMPLE 1 Preparation of Adhesion Promoter Including Zirconium Chelate

To a round bottomed flask equipped with a stirrer and a condenser, 4.70 g (10.0 mmol) of tetra n-propyl zirconate (TNPZ) was charged along with 5.00 g (20.0 mmol) of a mixture of citric acid, mono-ethyl citrate, di-ehthyl citrate and tri-ethyl citrate (hereafter referred to as “Mixture 1”). The total mole of Mixture 1 is around 20.0 mmol, and the carboxylic acid number of Mixture 1 is around 200 mg KOH/g. The ratio of the total mole of Mixture 1 to the mole of TNPZ is about 2:1. The resulting solution was heat to 80° C. and was stirred for 30 minutes. A clear and light-yellow liquid, Product 1A, was obtained. Product 1A has a Gardner color scale of 3-5 and a Brookfield viscosity (No. 3 spindle at 60 rpm) of 30-200 mPa·s at 25° C. Other zirconium chelates (Products 1B-1D) were also made by the processes described above, but the reactants used for producing Products 1B-1D were different from that for Product 1A. The reactant, Mixture 2, for producing Products 1C and 1D is the mixture of malic acid, mono-ethyl malate, and di-ethyl malate. The total mole of Mixture 2 is around 20.0 mmol, and the carboxylic acid number of Mixture 2 is around 300 mg KOH/g. The reactants used for producing Products 1A-1D are listed in the following Table 1, in which TNBZ is an abbreviation of tetra-n-butyl zirconate. The Mixture 1 and the Mixture 2, TNPZ, and TNBZ are collected from the market.

TABLE 1 Product 1A Product 1B Product 1C Product 1D Metal alkoxide TNPZ TNBZ TNPZ TNBZ (4.70 g) (4.70 g) (4.70 g) (4.70 g) Mixture Mixture 1 Mixture 1 Mixture 2 Mixture 2 (5.00 g) (5.00 g) (3.30 g) (3.30 g)

EXAMPLE 2 Preparation of Adhesion Promoter Including Titanium Chelate

To a round bottomed flask equipped with a stirrer and a condenser, 3.50 g (12 mmol) of tetra i-propyl titanate (TIPT) was charged along with 6.00 g (24 mmol) of Mixture 1. The ratio of the total mole of the Mixture 1 to the mole of the TIPT is about 2:1. The resulting solution was stirred for 30 minutes. A light yellow liquid, Product 2A, was obtained. Other titanium chelates (Products 2B-2D) were also made by the processes described above, but the reactants used for producing Products 2B-2D were different from that for Product 2A. The reactants used for producing Products 2A-2D are listed in the following Table 2, in which TNPT is an abbreviation of tetra-n-propyl titanate. The Mixture 1, the Mixture 2, TIPT, and TNPT are collected from the market.

TABLE 2 Product 2A Product 2B Product 2C Product 2D Metal alkoxide TIPT TNPT TIPT TNPT (3.50 g) (3.50 g) (3.50 g) (3.50 g) Mixture of Mixture 1 Mixture 1 Mixture 2 Mixture 2 citric acid and (6.00 g) (6.00 g) (4.00 g) (4.00 g) alkyl citrates

EXAMPLE 3 Preparation of Ink Composition

The compositions used for forming Inks 1-7 are listed in the following Table 3, in which Ink 1 and 2 are comparative examples, and Ink 7 is control example. Ink 1 was prepared by the following steps. A dispersion including denatured ethanol (18.5 g), ethyl acetate (27.5 g), nitrocellulose (9.5 g), resin VariPlus SK (2.0 g), and polyurethane resin (15.0 g) was stirred and heat to 50-60° C., and then TiO₂ (27.5 g) was added to the dispersion. Subsequently, an adhesion promoter, VERTEC™ P12 (2.5 g), was added to form Ink 1. Other ink compositions (Inks 2-7) were also formed by the processes described above; however, the adhesion promoters used for forming Inks 2-6 were different from that for Ink 1, and Ink 7 does not include any adhesion promoter. In Table 3, the nitrocellulose was obtained from T. N. C. Industrial Co., Ltd., and its trade name is SS 1/8. The polyurethane resin was obtained from Morchem, and its trade name is TP629. VERTEC™ P12 and VERTEC™ IA10 are commercial adhesion promoters.

TABLE 3 Ink 1 Ink 2 Ink 3 Ink 4 Ink 5 Ink 6 Ink 7 Solvent Denatured 18.5 18.5 18.5 18.5 18.5 18.5 18.5 ethanol (g) Ethyl acetate (g) 27.5 27.5 27.5 27.5 27.5 27.5 27.5 Polymeric Nitrocellulose (g) 9.5 9.5 9.5 9.5 9.5 9.5 9.5 binder Resin VariPlus SK (g) 2.0 2.0 2.0 2.0 2.0 2.0 2.0 Polyurethane 15.0 15.0 15.0 15.0 15.0 15.0 15.0 resin (g) Pigment TiO₂ (g) 27.5 27.5 27.5 27.5 27.5 27.5 27.5 Adhesion VERTEC ™ PI2 (g) 2.5 NA NA NA NA NA NA promoter VERTEC ™ NA 2.5 NA NA NA NA NA IA10 (g) Product 1A (g) NA NA 2.5 NA NA NA NA Product 1C (g) NA NA NA 2.5 NA NA NA Product 2A (g) NA NA NA NA 2.5 NA NA Product 2C (g) NA NA NA NA NA 2.5 NA Total weight (g) 102.5 102.5 102.5 102.5 102.5 102.5 100

EXAMPLE 4 Adhesion Test of Ink Composition

Inks 1-7 were printed on an oriented polypropylene film treated by corona-discharge. The printed film was dried. The adhesion of each of Inks 1-7 was tested after different storage time. The adhesion test includes the following steps. An adhesive tape (18 mm wide) is applied to cover the surfaces of Inks 1-7 to ensure the test conditions are identical. After a period of storage time, the adhesive tape is removed from the surfaces of Inks 1-7 simultaneously, and results are determined by the percentage ink remaining in the total test area after removal of the adhesive tape. The adhesion test results are shown in the following Table 4.

TABLE 4 Storage time 1 min 5 min 15 min 30 min 60 min Ink 1 40% 60% 75% 90% 95% Ink 2 14% 26% 27% 32% 40% Ink 3 50% 55% 60% 80% 85% Ink 4 20% 39% 45% 58% 82% Ink 5 39% 42% 52% 74% 80% Ink 6 15% 29% 40% 70% 75% Ink 7 5% 8% 10% 12% 15%

EXAMPLE 5 Odor Test, Color Test, and Wet Crinkle Test of Ink Composition

In the odor test, Inks 1-7 were printed on different oriented polypropylene films treated by corona-discharge respectively. The printed films were dried and then respectively stored in sealed glass jars for 24 hours at 40° C. The odor of each of Inks1-7 was assessed by a panel of 5 people on a scale from 1 (no perceptible odor) to 5 (very strong odor). The data are averaged and then rounded to the nearest whole number, and the results are listed in the following Table 5.

In the color test, Inks 1-7 were printed on different oriented polypropylene films treated by corona-discharge respectively. The printed films were dried and then respectively stored in sealed glass jars for 24 hours at 40° C. The color of each of Inks 1-7 was assessed by a panel of 5 people on a scale from 1 (no perceptible color) to 5 (severe yellow color). The data are averaged and then rounded to the nearest whole number, and the results are listed in the following Table 5.

Further, the wet crinkle test is used to assess adhesion when a printed film is wet. In the wet crinkle test, Inks 1-7 were printed on different oriented polypropylene films treated by corona-discharge respectively. The printed films were dried, and then were rubbed between the knuckles several times under cold running water. The wet crinkle resistance of each of Inks 1-7 was assessed visually by observing the undamaged remaining ink in the test area by a panel of 5 people on a scale from 1 (no ink removal) to 5 (severe removal). The data are averaged and then rounded to the nearest whole number, and the results are listed in the following Table 5.

TABLE 5 Odor test Color test Wet crinkle test Ink 1 4 5 1 Ink 2 1 1 2 Ink 3 1 1 1 Ink 4 2 1 1 Ink 5 2 1 1 Ink 6 2 1 1 Ink 7 1 1 4

From Table 5, it can be seen that Inks 3, 4, 5, and 6, which include the adhesion promoters prepared by acid ester mixture, are odorless and colorless, and show good wet crinkle resistance.

In view of the foregoing, the present disclosure provides ink compositions and adhesion promoters for use in ink composition. The adhesion promoters include a reaction product of a metal alkoxide and an acid ester mixture. The acid ester mixture may further include water. The manufacturing process of the adhesion promoters do not need any purification step and are simple. Moreover, the ink compositions including the adhesion promoter of the present disclosure are odorless and colorless and show good wet crinkle resistance. It is noted that the adhesion promoters include a mixture of many kinds of metal chelates, and therefore the properties of the adhesion promoters can be easily adjusted to meet various requirements.

Although the present invention has been described in considerable detail with reference to certain embodiments thereof, other embodiments are possible. Therefore, the spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.

It will be apparent to those skilled in the art that various modifications and variations can be made to the structure of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention cover modifications and variations of this invention provided they fall within the scope of the following claims. 

What is claimed is:
 1. An adhesion promoter comprising a reaction product of: (A) a metal alkoxide having a formula of M(OR₁)(OR₂)(OR₃)(OR₄), wherein M is titanium, zirconium, or aluminum, and R₁, R₂, R₃, and R₄ are independently C₁ to C₈ alkyl group; and (B) a mixture of at least one alpha hydroxy acid and at least one alpha hydroxy acid ester, wherein the alpha hydroxy acid is selected from the group consisting of glycolic acid, lactic acid, malic acid, tartaric acid, and citric acid, and the alpha hydroxy acid ester is selected from the group consisting of glycolic acid ester, lactic acid ester, malic acid ester, tartaric acid ester, and citric acid ester.
 2. The adhesion promoter of claim 1, wherein the alpha glycolic acid ester has a formula of CH₂OH(COOR₅), and R₅ is C₂ to C₆ alkyl group.
 3. The adhesion promoter of claim 1, wherein the alpha lactic acid ester has a formula of C₂H₄OH(COOR₆), and R₆ is C₂ to C₆ alkyl group.
 4. The adhesion promoter of claim 1, wherein the alpha malic acid ester has a formula of C₂H₃OH(COOR₇)(COOR₅), R₇ and R₈ are independently H atom or C₂ to C₆ alkyl group, and one of R₇ and R₈ is an alkyl group.
 5. The adhesion promoter of claim 1, wherein the alpha tartaric acid ester has a formula of C₂H₂(OH)₂(COOR₉)(COOR₁₀), R₉ and R₁₀ are independently H atom or C₂ to C₆ alkyl group, and one of R₉ and R₁₀ is an alkyl group.
 6. The adhesion promoter of claim 1, wherein the alpha citric acid ester has a formula of C₃H₄OH(COOR₁₁)(COOR₁₂)(COOR₁₃), R₁₁, R₁₂ and R₁₃ are independently H atom or C₂ to C₆ alkyl group, and one of R₁₁, R₁₂ and R₁₃ is an alkyl group.
 7. The adhesion promoter of claim 1, wherein the mixture further comprises water.
 8. The adhesion promoter of claim 1, wherein the mixture has a carboxylic acid number of from about 50 mg KOH/g to about 400 mg KOH/g.
 9. The adhesion promoter of claim 1, wherein a ratio of a total mole of the at least one alpha hydroxy acid and the at least one alpha hydroxy acid ester to a mole of the metal alkoxide is 0.2 to 4:1.
 10. An ink composition comprising: a pigment; a polymeric binder; a solvent for the polymeric binder; and the adhesion promoter of claim
 1. 11. The ink composition of claim 10, wherein the adhesion promoter is present at a concentration of from 1% to 20% by weight, based on the total weight of the ink composition.
 12. The ink composition of claim 10, wherein the polymeric binder has at least one functional group selected from the group consisting of hydroxyl group (—OH), amino group (—NH₂), carboxyl group (—COOH), cyanate group (—NCO), and ester group. 